Recovery of rare earth elements and compounds from coal ash

ABSTRACT

The coal ash can be sorted into groups of substantially unburned carbon and substantially burned carbon. The substantially unburned carbon or the substantially burned carbon can be magnetically treated to cause separation into a substantially magnetic portion and a substantially non-magnetic portion. The substantially magnetic portion or the substantially non-magnetic portion can be filtered into a substantially course portion and a substantially fine portion. The substantially coarse portion or the substantially fine portion can be treated with a mineral acid to form an aqueous mineral acid solution. The aqueous mineral acid solution can be extracted to form an organic solution that includes the rare earth salts. The organic solution can be mixed with water to form an aqueous solution that includes the rare earth salts. The rare earth salts can be separated from the aqueous solution.

CROSS-REFERENCE TO RELATED APPLICATIONS

This instant application is a continuation-in-part of U.S. patentapplication Ser. No. 13/864,677, filed on Apr. 17, 2013 and titled“Recovery of Rare Earth Elements and Compounds from Coal Ash,”, whichclaims the benefit of and priority to U.S. provisional patentapplication No. 61/625,292, filed Apr. 17, 2012, the entire contents ofwhich are incorporated by reference herein and owned by the assignee ofthe instant application.

FIELD OF THE INVENTION

The invention relates generally to recovery of rare earth elementsand/or compounds from coal ash.

BACKGROUND

Rare earth elements can be fundamental to emerging green energytechnologies in the United States (e.g., permanent magnet motors forwind turbines and disk drives, hybrid car batteries, compact fluorescentlighting, and/or displays in all types of consumer/defense electronics),as well as other usages such as industrial catalysts for refiningheavier crude oil, automobile catalytic converters, and/or as alloyingelements. Presently, rare earth elements can be obtained through mining.

Coals from certain regions of the world can be particularly rich in rareearth elements, approaching a total concentration of about 1000parts-per-million (“ppm”). The combustion of coal in power plants forenergy generation concentrates non-volatile minerals in the ash by aboutten times, to about 10,000 ppm, or on the order of approximately 1%.Coal ash can be the product of burning coal. Coal ash can be comprisedof fly ash and bottom ash. Fly ash can be ash that rises with fluegases. Bottom ash can be ash that is found at the bottom of a furnace.Fly ash can be collected before the flue gases reach chimneys of powerplants.

A method to extract rare earth elements from coal is desired. The UnitedStates alone produces on the order of 100 million metric tons of fly ashannually. Accounting for process yield and variability in rare earthelement content, if rare earth elements are extracted from coal ash, areasonable fraction of currently available fly ash (e.g., about 10-15%)can be adequate to meet rare earth elements demand in the United States.

SUMMARY OF THE INVENTION

Advantages of the invention include recovering rare earth elements fromcoal ash. Another advantage of the invention includes economicalproduction of rare earth elements and/or compounds from alternative,non-mineral raw materials. Another advantage of the invention is theability to build reliable production capabilities and/or supply chainfor rare earth elements and/or byproducts. Another advantage of theinvention is processing fly ash to recover rare earth materials,particularly heavier rare earths, more economically andenergy-efficiently per kilogram of rare earth elements than fromprocessing and extracting mineral resources. Another advantage includesthe beneficiation of coal ash, which is an abundant waste material, forrecovering economically useful and marketable industrial materials thatinclude rare earth elements as a significant component. Anotheradvantage includes energy efficient extraction of rare earth elements,which can save energy use by about 75% relative to conventional miningper unit weight of rare earth elements produced. Yet another advantageis the accompanying carbon dioxide (CO₂) emission can be lower thanmining by about 75%. Still another advantage includes production ofenvironmentally beneficiated ash cake, which can be free of hazardouselements.

In one aspect, the invention involves a method of recovering rare earthelements from coal ash. The method involves sorting the coal ash intogroups of substantially unburned carbon and substantially burned carbon.The substantially unburned carbon or substantially burned carbon ismagnetically treated to cause separation into a substantially magneticportion and a substantially non-magnetic portion. The substantiallymagnetic portion or the substantially non-magnetic portion is filteredinto a substantially course portion and a substantially fine portion.The substantially coarse portion or the substantially fine portion istreated with a mineral acid to form an aqueous mineral acid solutionthat contains rare earth element salts. The aqueous mineral acidsolution is extracted to form an organic solution that includes the rareearth salts. The organic solution is mixed with water to form an aqueoussolution that includes the rare earth salts and the rare earth salts (orrare earth elements) are separated from the aqueous solution.

The aspect described above can include one or more of the followingfeatures. In some embodiments, sorting the coal ash can includescreening the coal ash to collect coal ash that is smaller than a firstpredefined size. Sorting the coal ash can also include performing frothfloatation of the screened coal ash. The coal ash that does not floatcan be gathered.

In various embodiments, screening the coal ash can be done using ascalping screen. The substantially non-magnetic portion of the coal ashcan be filtered by size. In some embodiments, cyclone separating removescoal ash that is smaller than a second predefined size. Thesubstantially fine portion of the coal ash can be smaller than thesecond predefined size. The substantially fine portion of the coal ashcan be removed and used in a cement substitute market.

In some embodiments, the substantially coarse portion of the coal ash istreated with a mineral acid. The mineral acid can be nitric acid.

In various embodiments, treating includes heating the mineral acid toapproximately 90° C. The substantially coarse portion, the substantiallyfine portion, or both can be exposed to the mineral acid for at leastone hour. Exposing the coal ash can include additional heating of aresulting solution formed when exposing the coal ash to the mineral acidto generate a more concentrated mixture.

In some embodiments, extracting the aqueous mineral acid solution alsoincludes mixing the aqueous mineral acid solution with tributylphosphate and kerosene. Extracting the aqueous mineral acid solution canalso include removing the organic solution from the aqueous mineral acidsolution such that the rare earth salts are substantially removed alongwith the organic solution. Extracting the aqueous mineral acid solutioncan further include performing a dry extraction, a liquid extraction, orany other combination. The dry extraction can be a Soxhlet extraction.The dry extraction can also include performing continuous extraction ofrare earth salts with tributyl phosphate.

In various embodiments, mixing the organic solution includes performingmultiple cycles of mixing the organic solution with water until aconcentration level of rare earth salts in the aqueous solution is belowa predetermined threshold. In other embodiments, magnetically treatingcan include ion exchange separation. Ion exchange separation leading torare earth element mixtures can be converted to mixtures of rare earthoxides and rare metals for various applications such as catalyst,magnets, and phosphor applications.

Other aspects and advantages of the invention will become apparent fromthe following detailed description, taken in conjunction with theaccompanying drawings, illustrating the principles of the invention byway of example only.

BRIEF DESCRIPTION OF THE DRAWINGS

The advantages of the invention described above, together with furtheradvantages, may be better understood by referring to the followingdescription taken in conjunction with the accompanying drawings. Thedrawings are not necessarily to scale, emphasis instead generally beingplaced upon illustrating the principles of the invention.

FIG. 1 is a flow diagram of a method for extraction of rare earthelements from coal ash, according to an illustrative embodiment of theinvention.

FIG. 2 is flow diagram of a method for treatment of coal ash, accordingto an illustrative embodiment of the invention.

FIG. 3 is a flow diagram of a method for extraction of aqueous mineralacid solution, according to an illustrative embodiment of the invention.

FIG. 4 is a flow diagram of a method for mixing organic solution,according to an illustrative embodiment of the invention.

FIG. 5 is a flow diagram of a method for separation of rare earthelements, according to an illustrative embodiment of the invention.

FIG. 6 is a flow diagram of a method for extraction of rare earthelements from coal ash, according to an illustrative embodiment of theinvention.

FIG. 7 is flow diagram of a method for sorting coal ash, according to anillustrative embodiment of the invention.

DETAILED DESCRIPTION OF THE INVENTION

A method of processing coal ash can be used to recover rare earthelements in order to, for example, meet critical rare earth elementmaterials needs. The method can employ a closed looped schema e.g.,certain materials, such as aqueous mineral acid, can be reused ratherthan discharged as waste. Since materials are reused, the closed-loopschema can have a lower environmental impact than, for example, miningfor rare earth elements.

The method can also allow exploitation of low grade sources of the rareearth elements. The method can utilize waste ash, e.g., ash that followscoal combustion, as a resource for rare earth elements. The method canallow beneficiating the waste ash while simultaneously recovering rareearth elements.

Rare earth elements principally include the lanthanide series of theperiodic table, but the term can also incorporate scandium and yttriumthat are not true lanthanides. Exemplary rare earth elements, include:lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd),promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium(Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm),ytterbium (Yb), lutetium (Lu), scandium (Sc) and yttrium (Y). Rare earthelements can include light rare earth elements, medium rare earthelements, and/or heavy rare earth elements. Exemplary light rare earthelements include Sc, La, Ce, Pr, Nd, and Pm. Exemplary medium rare earthelements include Sm, Eu, and Gd. Exemplary heavy rare earth elementsinclude Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y.

Rare earth elements that are recovered from coal can have a number ofapplications. For example, some of these coals contain Y, a heavy rareearth element that can be used in compact fluorescent light bulbs. Thecoals can also contain Nd, a light rare earth element that can be usedin permanent magnet motors in hybrid vehicles, wind turbines, andcomputer disk drives. Other applications for rare earth elements caninclude, for example, use in aerospace components, high refractive indexglass, flint, batteries, catalysts, polishes, lasers, x-ray machines andcapacitors.

FIG. 1 shows a flow diagram of a method 100 for extraction of rare earthelements from coal ash, according to an illustrative embodiment of theinvention. The method 100 involves treating coal ash (e.g., mineral aciddigestion) that includes rare earth elements (rare earth elements may bereferred to as rare earth element salts) with a mineral acid to form anaqueous mineral acid solution (Step 104). The method also involvesextracting the aqueous mineral acid solution to form an organic solutionthat includes the rare earth elements (Step 108). The method alsoinvolves mixing the organic solution with water to form an aqueoussolution that includes the rare earth elements (Step 112). The methodalso involves separating the rare earth elements from aqueous solution(Step 116). The method 100 can be a solvent extraction process. In someembodiments, the solvent extraction process uses a mineral acid that canbe recovered and recycled to extract the rare earth elements from coalash.

In some embodiments, fly ash is used to extract the rare earth elements(as opposed to coal ash, which contains both fly ash and bottom ash).Although fly ash and coal ash are not necessarily the same, any of thepreceding and/or foregoing methods applied to fly ash can be applied tocoal ash and vice versa. In various embodiments, any of the precedingand/or foregoing methods applied to fly ash and/or coal ash can also beapplied to bottom ash.

In some embodiments, the mineral acid is nitric acid. In variousembodiments, the rare earth element is a rare earth nitrate and theaqueous mineral acid solution is an aqueous nitric acid solution. Insome embodiments, the mineral acid is selected based on a specificapplication for the rare earth elements. For example, nitric acid (7M)can be used in a PUREX (Plutonium—Uranium Extraction) process (e.g., aprocess for the reprocessing of spent nuclear fuel to separate uraniumand plutonium from the fission products and from one another) becausethe nitric acid can be used to dissolve used nuclear fuel. In someembodiments, the mineral acid is different from the hydrochloric and/orsulfuric acid mineral acids that are typically used for rare earthelement extraction directly from mined minerals.

FIG. 2 shows a flow diagram for a method 200 for the treatment of coalash (e.g., Step 104 as described above in FIG. 1), according to anillustrative embodiment of the invention. The method 200 involvespreprocessing the coal ash (Step 204). The preprocessing can beperformed to concentrate the coal ash and can be either a physicalpreprocessing or a chemical preprocessing. Concentrating the coal ashcan involve exposing the coal ash to magnetic treatment (e.g., magneticseparation). Magnetic separation is a physical preprocessing that cancreate a magnetic fraction that includes a substantially magneticfraction and a substantially nonmagnetic fraction. Other types ofpreprocessing of the coal ash can occur, including other physicalpreprocessing, such as sieving (e.g., separating out a particle sizerange that does not contain the rare earth elements), and/or chemicalpreprocessing, such as froth floatation (e.g., modifying the surfaceproperties of rare earth elements that containing certain compounds suchthat the rare earth elements float to the top of a preprocess tank orsink to the bottom of the tank (reverse floatation)).

Magnetic treatment can maximize efficiency of extracting the rare earthelements from coal ash by, for example, passing the coal ash through amagnetic separator before chemical processing. Certain types of coal ashcan contain significant concentrations of magnetic iron oxides. Forexample, coal ash created from coals mined in Kentucky and/or countriessuch as Bulgaria can be particularly rich in magnetic iron oxides. Byknowing which oxide is likely concentrated in a particular type of coalash, magnetic separation can be used to concentrate the rare earthelements (e.g., produce a substantially magnetic portion of coal ash).For example, if the rare earth elements found in fly ash are tied intomagnetic spinal/glass structures, then the rare earth elements can beseparated into the magnetic fraction. If the rare earth elements foundin fly ash are not tied into magnetic spinal/glass structures, then therare earth elements, which exist in their oxide forms in the coal ash,can separate into the non-magnetic fraction. Sampling and testing can bedone to determine whether the rare earth elements are in the magnetic ornon-magnetic fractions by, for example, using glow discharge massspectroscopy. Magnetic structures used to facilitate the magneticseparation can include magnetite (Fe₃O₄), hematite (Fe₂O₃), and/or otheriron oxides such as gamma-Fe₂O₃ or maghemite.

The method 200 also involves heating a mineral acid (Step 212). Themineral acid can be a volume of 3 Normal (N) mineral acid. The mineralacid can be heated to approximately 90° C. In some embodiments, themineral acid can be heated at any temperature between 60° C. and 95° C.The method 200 also involves exposing the coal ash to the mineral acid(Step 216). In some embodiments, the coal ash is exposed to the mineralacid for at least one hour. Exposing the coal ash to the mineral acidcan concentrate the amount of rare earth elements that are found in thecoal ash. In some embodiments, after the coal ash is exposed to mineralacid, the coal ash is heated and exposed to the mineral acid again(e.g., repeat Steps 212 and 216, respectively). In various embodiments,the number of times the coal ash is heated and exposed to mineral acidcan be 1, 2, 3, or any number of times. The type of rare earth elementor coal ash source can determine the number of times the coal ash isheated and exposed to mineral acid. Additional heating (e.g., at ahigher temperature and/or heating for a longer duration) of the mixtureof the mineral acid and coal ash can generate a more concentratedmixture. A more concentrated mixture can contain more rare earth elementthen would occur if the additional heating was not applied. A resultingproduct of Step 216 can include an aqueous mineral acid solution, ashcake and gas.

FIG. 3 shows a flow diagram for a method 300 for the extraction ofaqueous mineral acid solution, according to an illustrative embodimentof the invention (e.g., Step 108 as described above in FIG. 1). Themethod 300 involves extracting treated coal ash (Step 308). Treated coalash can be the product of procedures such as Step 104 or method 200. Thetreated coal ash can include an aqueous mineral acid solution, ash cakeand/or gas. The method 300 can involve mixing the aqueous mineral acidsolution from the treated coal ash with tributyl phosphate and keroseneand removing the organic solution from the aqueous mineral acid solutionsuch that rare earth salts are substantially removed with the organicsolution. In some embodiments, solutions such as ionic liquids,pivaloyltrifluoroacetone (HA),N-methyl-N-phenyl-1,10-phenanthroline-2-carboxamide (MePhPTA),1,4,10,13-Tetrathia-7,16-diazacyclooctadecane (ATCO) and/or ATCO binaryextraction systems containing lauric acid can be used to mix with theaqueous mineral acid solution from the treated coal ash instead oftributyl phosphate and kerosene.

Treated coal ash, such as the product of procedures such as Step 104 ormethod 200, can be subjected to an extraction method in Step 308. Theextraction method can be a dry extraction, a liquid extraction or acombination of the dry extraction and the liquid extraction. The dryextraction can be done using Soxhlet extraction. The dry extraction caninclude the pre-concentration of the aqueous mineral acid solution suchthat a higher concentration of rare earth elements is present in theaqueous mineral acid solution. The pre-concentration can be performed inany manner known to those of skill in the art, including drying, whichcan enable, for example, continuous extraction of rare earth elementsfrom dry rare earth salt concentrate and continuous recovery/recyclingof tributyl phosphate. In some embodiments, to minimize the amount oftributyl phosphate used in the extraction process, tributyl phosphatecan be recovered after the extraction process and recycled in a futureextraction process. This approach can have economic and environmentalbenefits. Other steps to further concentrate the rare earth salt can bedone to, for example, obtain higher yield efficiency.

In some embodiments, if dry extraction is used, the method 300 alsoinvolves continuously extracting (Step 320). In Step 320, rare earthsalts can be extracted from the aqueous mineral solution of treated coalash by capturing rare earth salts that are carried off in vapors formedby boiling tributyl phosphate mixed with the aqueous mineral solution.Mixing the aqueous mineral solution and tributyl phosphate can create asolution containing an organic solution and a mineral solution. In someembodiments, the vapors pass through an extraction chamber. Theextraction chamber can separate the rare earth salts from the vapors byallowing only the vapor to pass through to a condenser. The rare earthsalts can be collected in a ceramic or tissue paper thimble. The vaporsthat have passed through the extraction chamber can be converted backinto the aqueous mineral solution at the condenser. The aqueous mineralsolution collected at the condenser can be reintroduced and re-boiled.

Step 320 can be repeated until a threshold for an amount orconcentration of extracted rare earth salts is met. The threshold canbe, for example, an amount (e.g., mass/weight) of extracted rare earthsalt or a concentration of rare earth salt in the collected aqueousmineral solution. Step 320 can also be performed for a pre-determinedperiod of time. The period of time can be, for example, minutes, hours,days, etc. In some embodiments, the period of time can be a function ofa rare earth element concentration in the organic solution. PerformingStep 320 multiple times can be desired to ensure that a desired amountof rare earth salts is extracted from the aqueous mineral solution. Ifdry extraction is used, the method 300 can also involve diluting (Step328). In some embodiments, the organic solution formed in Step 320 isdiluted using kerosene.

In various embodiments, if liquid extraction is used, the method 300involves mixing (Step 332). The aqueous mineral acid solution of treatedcoal ash can be mixed with tributyl phosphate and kerosene. Mixing theaqueous mineral acid solution can create an aqueous mineral solutionthat contains little to no rare earth elements and an organic solutionthat contains rare earth elements. If liquid extraction is used, themethod 300 can also involve removing the organic solution (Step 336). Insome embodiments, the organic solution is removed from the aqueousmineral acid.

In various embodiments, the volume of tributyl phosphate and keroseneused in Step 332 is equal to the volume of aqueous mineral acidsolution. In various embodiments, the volume of tributyl phosphate andkerosene used in Step 332 is equal to a predetermined amount that isgreater than the volume of the aqueous mineral acid solution. Thepredetermined amount can be equal to any integer. For example, thepredetermined amount can be equal to 9, rendering the total volume usedin Step 332 to be 10× the volume of aqueous mineral acid solution. Insome embodiments, the volume of tributyl phosphate and the volume ofkerosene are equal. In various embodiments, the total volume of tributylphosphate and kerosene is equal to the predetermined amount greater thanthe volume of aqueous mineral acid solution (including situations wherethe predetermined amount is 1; e.g., when the volume of aqueous mineralacid solution is the same as the volume of tributyl phosphate andkerosene).

The initial concentrations of rare earth elements or salts in the coalash mineral acid extract can affect an extraction efficiency of the rareearth element recovery process, particularly in the efficiency-limitedextraction into tributyl phosphate/kerosene steps, such as in Step 332.For example, a six to ten fold increase in the initial concentration canincrease the extraction efficiency by over two-fold, depending on thespecific rare earth elements found in the coal ash mineral acid extract.For example, the coal ash mineral acid extract can be concentrated todryness and then re-dissolved in 3 Molar (M) mineral acid. In addition,the extraction into tributyl phosphate/kerosene steps, as describedabove, can be stirred continuously overnight, followed by a phaseseparation to improve the efficiency of extraction. Continuous stirringcan yield greater chances of removing all of or a significant portion ofthe rare earth elements from the aqueous mineral solution, such that theorganic solution can contains all of or a significant portion of therare earth elements that were originally in the aqueous mineralsolution.

In some embodiments, an efficiency of the extraction into tributylphosphate/kerosene steps can be increased by adding three times a volumeof 80/20 tributyl phosphate/kerosene (e.g., a mixture with a volume madeup of 80% tributyl phosphate and 20% kerosene) to the aqueous mineralacid solution. For example, using an initial concentration of 2× of theaqueous mineral acid solution prior to extraction into a 50-50 wt %tributyl phosphate/kerosene mixture may not have an effect on theefficiency of the rare earth element extraction. However, increasing theconcentration of the aqueous mineral acid solution after treating coalash with mineral acid and before extraction into tributylphosphate/kerosene by evaporation with water can increase theconcentration by 6× to 10× over the baseline, depending on the specificrare earth elements found in the coal ash. For example, theconcentration of aqueous mineral acid solution can be increased byadding three times the volume of tributyl phosphate/kerosene to theaqueous mineral acid solution (e.g., a 80-20 wt % mixture with a volumemade up of 80% tributyl phosphate/kerosene and 20% aqueous mineral acidsolution).

This process of concentrating the aqueous nitrate solution byevaporation can significantly increase the extraction efficiency,particularly with respect to the heavy rare earth elements yttrium anddysprosium and also for the light rare earth elements such as samarium.To improve the extraction efficiency further, the initial concentrationcan be further increased by water evaporation. Evaporation can be usedall the way to dryness (e.g., all water has been evaporated).

In addition, the extraction into tributyl phosphate/kerosene steps, suchas in Step 320, can be stirred continuously overnight, followed by phaseseparation to improve the efficiency of extraction.

A product of method 300 can include an organic solution that includesrare earth salts and thorium salts, and an aqueous mineral acid solutionwith rare earth salts and thorium salts removed (e.g., a second aqueousmineral acid solution different from the aqueous mineral acid found inthe resulting product of Step 216). Other hazardous element salts can beremoved as a result of method 300. In some embodiments, the secondaqueous mineral acid solution is distilled to recover mineral acid. Therecovered mineral acid can be recycled and used to treat coal ash.Recycling mineral acid can contribute to making the recovery of rareearth elements more economical. The product of method 300 can resultfrom either dry extraction or liquid extraction.

FIG. 4 shows flow diagram for a method 400 for mixing organic solution,according to an illustrative embodiment of the invention (e.g., Step 112as described above in FIG. 1). The method 400 can involve separating(Step 408). A solution, such as the product of method 300, can beintroduced into the method 400. In Step 408, organic solution can beseparated from other types of solution in the solution introduced intomethod 400 (e.g., an aqueous mineral acid solution). The organicsolution that is separated in Step 408 can include rare earth salts.Step 408 can use any type of liquid separation method, including phaseseparation, evaporation, and/or other similar methods.

Phase separation can be conducted in a separator where organic solutionseparates to the top of the mixture and the aqueous solution separatesfrom the organic solution to the bottom of the mixture. The separatedorganic solution can be re-extracted into water or re-extracted withdilute mineral acid to increase an extraction efficiency. The liquidused for re-extraction can be selected based on a determination of whichliquid yields a better extraction efficiency. The organic solution thatincludes thorium salts and aqueous solutions that includes rare earthsalts only can be separated from one another after re-extraction.

In some embodiments, the method 400 also involves mixing (Step 412). Theorganic solution can be mixed with water to form an aqueous solutionwith rare earth salts and organic solution without rare earth salts. Theaqueous solution can be removed resulting in a solution that issubstantially organic solution. In some embodiments, a saltconcentration check is performed on the substantially organic solution.If the substantially organic solution contains a concentration level ofrare earth salts above a predefined threshold, Step 412 can be repeated.Step 412 can be repeated as many times as needed (e.g., until the saltconcentration of the substantially organic solution is below thepredefined threshold). The predefined threshold can be a ratio of thesalt concentration in the organic solution versus the salt concentrationin the aqueous solution. In some embodiments, the ratio can be 1:10 or1:100. The ratio can also be dependant on the type of rare earth saltthat is being mixed. The threshold can also be dependant on whether itis monetarily worth extracting the rare earth slats at lowconcentrations.

FIG. 5 shows a flow diagram for a method 500 for separation rare earthelements, according to an illustrative embodiment of the invention(e.g., Step 116 as described above in FIG. 1). In some embodiments, themethod 500 involves ion exchange (Step 504). Rare earth salts can beseparated from an aqueous solution using ion exchange. Ion exchangeseparation can only be used for the separation of rare earth elementsfrom mixtures that contain small amounts of rare earth elements. Ionexchange can use anion or cation exchange.

The method 500 can also involve converting the rare earth salts intomixtures in (Step 508). These mixtures can include rare earth oxides orrare earth metals. The mixtures can include pre-selected nitratessuitable for specific applications. Specific applications can includecatalyst applications 512, magnets applications 516 and phosphorapplications 520. In some embodiments, the process 500 separates therare earth nitrites into individual rare-earth nitrates, such as Y, La,Ce, Nd, Dy, etc.

In some embodiments, ion exchange also includes concentrating theaqueous solution to dryness and then dissolving dried solution in asolution containing 5% 7M mineral acid and 95% methanol. The dried saltsolution can be loaded into an ion exchange column where it can bewashed with a solution containing 5% 7M mineral acid and 95% methanolbefore undergoing ion exchange separation. In various embodiments, driedsalt solutions enriched in heavy rare earth elements are eluted with asolution containing 55% 7M mineral acid and 55% methanol. Dried saltsolutions enriched in light rare earth elements can be eluted withwater.

The separation of salt mixtures into various rare earth elements or rareearth salts forms instead of into specific rare earth oxides can haveseveral advantages. Going directly from an aqueous solution with rareearth salts to rare earth oxides can require heating at hightemperatures (e.g., about 700° C.) for a significant amount of time(e.g., about 1 hour). This high temperature process can require asignificant amount of energy. These various rare earth salt forms canlater be converted into separated forms of oxides but only if necessary.If an application does not require a specific oxide, there can be anenergy savings. An energy savings can amount to 1,200 J/g. In addition,ion exchange can remove other metal nitrate contaminants from thenitrate mixtures.

Process parameters (e.g., time, temperature, concentration) are nominalvalues and can be optimized by one of ordinary skill in the art toimprove the yields for rare earth elements from coal ash, depending on,for example, the concentration of rare earth elements in the coal ash.

Ash cake, or ash remainder, that can be formed in the process ofrecovering rare earth elements (e.g., the solid residue after mineralacid digestion) can be free of hazardous elements such as arsenic,cadmium, and thorium (e.g., hazardous elements are removed from the ashcake in the process of recovering rare earth elements). Coal ash thatdoes not go through the process of recovering rare earth elements canpresent an environmental hazard due to the presence of radioactivethorium and toxic elements such as, for example, arsenic and cadmium.The ash cake formed in this process as a by product can be moreenvironmentally friendly and therefore can be remediated or used inapplications such as a building or road construction material. Forexample, the ash cake can be used as a Portland cement substitute inconcrete. In some embodiments, toxic elements, such as arsenic, areremoved during mineral acid digestion steps (e.g., Step 600, asdescribed below). In other embodiments, radioactive elements, such asthorium, are removed during re-extraction (e.g., Step 620, as describedbelow).

FIG. 6 shows a flow diagram of a method 600 for extraction of rare earthelements from coal ash, according to an illustrative embodiment of theinvention. The method 600 involves additional steps to increase theconcentration of rare earth elements as described by method 100 (e.g.,the method 600 is the method 100 plus additional steps). Additionalsteps can be physical or chemical methods. These additional steps canincrease the efficiency of the chemical extraction or enrichment of flyash. Concentration of rare earth elements can be higher within aluminum,non-magnetic iron, or alunimosilicate glass. In various embodiments, theincrease in efficiency can be as much as 5 times or more.

The method 600 involves sorting coal ash that includes rare earthelements (Step 604). In some embodiments, Step 604 sorts coal ash intogroups of substantially unburned carbon and substantially burned carbon.Groups of substantially unburned carbon can be a mix of unburned andburned carbon in which there is more unburned carbon than burned carbon.Groups of substantially burned carbon can be a mix of unburned andburned carbon in which there is more burned carbon than unburned carbon.In some embodiments, groups of substantially unburned carbon contains80% or more unburned carbon in a mixture of unburned and burned carbon.In various embodiments, groups of substantially burned carbon contain80% or more burned carbon in a mixture of unburned and burned carbon.Additional details regarding Step 604 are described below by method 700.

The method 600 also involves magnetically treating the sorted coal ashto cause separation (Step 608). Step 608 can separate the coal ash intoa substantially magnetic portion and a substantially non-magneticportion. In some embodiments, the proportion of the substantiallymagnetic portion to substantially non-magnetic portion can be 80% ormore. The proportion of the substantially magnetic portion tosubstantially non-magnetic portion can depend on the type of materialthat makes up the substantially magnetic and the substantiallynon-magnetic portions. The proportion of the substantially magneticportion to substantially non-magnetic portion of a type of ash can alsodepend on where the coal originated from, in which coal from certainregions of the world may yield more or less substantially magneticportions. For example, ash from one region can yield an approximate 10%substantially magnetic portion, whereas ash from another region canyield an approximate 35% substantially magnetic portion. The separationcan be done using a magnet on the sorted coal ash to attract thesubstantially magnetic portion. Other forms of magnetic treatment caninclude any methodology using an electromagnetic field to draw out (orseparate) substantially magnetic material from non-substantiallynon-magnetic material.

The method 600 also involves filtering the magnetically treated coal ash(Step 612). Step 612 can filter the magnetically treated coal ash bysize. For example, coal ash can be separated by ash that is greater than75 microns, less than 25 microns and 25-75 microns. Filtering of Step612 can cause coal ash to separate into a substantially course portionand a substantially fine portion. Filtering of the magnetically treatedcoal ash can be done using a cyclone separator.

In some embodiments, the cyclone separator removes coal ash that issmaller than a predefined cyclone separator size. For example, thepredefined cyclone separator size can be in the range of +500 mesh, +200mesh, +60 mesh, +75 mesh, −60 mesh, −75 mesh, −200 mesh and −500 mesh.Fine coal ash can be smaller than the predefined cyclone separator size.Course coal ash can contain more crevices to hold rare earth elements.

In some embodiments where the coal ash is separated into a substantiallyfine portion, the substantially fine portion of coal ash is removed andused in a cement substitute market (e.g., the substantially fine portionof coal ash can be sold to be used as an ingredient or component forcement). The substantially fine portion can be mixed with water andevaporated to create pozzolanic fine ash. Pozzloanic fine ash containsaluminosilicates and other compounds which can be substitutes forconcrete. The substantially course portion of coal ash can be theportion of the coal ash that is treated with mineral acid (e.g., as inStep 616). Using coal ash as a cement substitute can lower cost forcement manufacturers as well as global CO₂ emissions, which is aby-product of the cement manufacturing process.

The method 600 also involves treating filtered coal ash (e.g., mineralacid digestion) with a mineral acid to form an aqueous mineral acidsolution (Step 616). The method also involves extracting the aqueousmineral acid solution to form an organic solution that includes the rareearth elements (Step 620). The method also involves mixing the organicsolution with water to form an aqueous solution that includes the rareearth elements (Step 624). The method also involves separating the rareearth elements from aqueous solution (Step 628). The method 600 can be asolvent extraction process. In some embodiments, the solvent extractionprocess uses a mineral acid that can be recovered and recycled toextract the rare earth elements from coal ash.

In some embodiments, Step 616 is the same as Step 104 as described abovein FIG. 1. Namely, Step 616 can involve treating coal ash (e.g., mineralacid digestion) that includes rare earth elements with a mineral acid toform an aqueous mineral acid solution. Step 620 can be the same as Step108 as described above in FIG. 1. Namely, Step 620 can involveextracting the aqueous mineral acid solution to form an organic solutionthat includes the rare earth elements. Step 624 can be the same as Step112 as described above in FIG. 1. Namely, Step 624 can involve mixingthe organic solution with water to form an aqueous solution thatincludes the rare earth elements. Step 628 can be the same as Step 116as described above in FIG. 1. Namely, Step 628 can involve separatingthe rare earth elements from aqueous solution.

FIG. 7 shows a flow diagram for a method 700 of sorting of coal ash(e.g., Step 604 as described above in FIG. 6), according to anillustrative embodiment of the invention. The method 700 involvesscreening the coal ash (Step 704). Screening can be performed to collectcoal ash of a certain size. In some embodiments, screening is done tocollect coal ash that is smaller than a predefined screening size. Forexample, the predefined screening size can be in the range of −200 to+500 mesh. Screening can be performed utilizing a scalping screen. Ascalping screen can have a +60 mesh (e.g., greater than 250 μm). Thescalping screen can also have a size of 500 mesh, +200 mesh, +75 mesh,−60 mesh, −75 mesh, −200 mesh and −500 mesh. As apparent to one ofordinary skill in the art, other forms of sorting (e.g., using avibratory conveyor) can also be performed to collect coal ash of acertain size.

The method 700 also involves preforming froth floatation (Step 708).Froth flotation can be done on the screened coal ash to separate thesubstantially burned carbon and the substantially unburned carbon. Theunburned carbon can be used in the activated carbon market. The method700 also involves gathering the coal ash (Step 712). Step 712 caninvolve gathering the coal ash that does not float (e.g., the tailings).

In some embodiments, the tailings from froth flotation are thesubstantially burned carbon, which are then magnetically treated.Magnetically treating the tailings can be done wet or dry. Thesubstantially magnetic portion can be used as a magnetic substitute inthe heavy media coal separation market.

One skilled in the art will realize the invention may be embodied inother specific forms without departing from the spirit or essentialcharacteristics thereof. The foregoing embodiments are therefore to beconsidered in all respects illustrative rather than limiting of theinvention described herein. Scope of the invention is thus indicated bythe appended claims, rather than by the foregoing description, and allchanges that come within the meaning and range of equivalency of theclaims are therefore intended to be embraced therein.

What is claimed:
 1. A method of recovering rare earth elements from coalash, the method comprising: sorting the coal ash into groups ofsubstantially unburned carbon and substantially burned carbon;magnetically treating at least one of the substantially unburned carbonor the substantially burned carbon to cause separation into asubstantially magnetic portion and a substantially non-magnetic portion;filtering at least one of the substantially magnetic portion or thesubstantially non-magnetic portion into a substantially course portionand a substantially fine portion; treating at least one of thesubstantially coarse portion or the substantially fine portion with amineral acid to form an aqueous mineral acid solution; extracting theaqueous mineral acid solution to form an organic solution that includesthe rare earth salts; mixing the organic solution with water to form anaqueous solution that includes the rare earth salts; and separating therare earth salts from the aqueous solution.
 2. The method of claim 1,wherein sorting the coal ash further comprises: screening the coal ashto collect coal ash that is smaller than a first predefined size;performing froth floatation of the screened coal ash; and gathering coalash that does not float.
 3. The method of claim 2, wherein screening thecoal ash further comprises utilizing a scalping screen.
 4. The method ofclaim 1, wherein the substantially non-magnetic portion of the coal ashis filtered by size.
 5. The method of claim 1, wherein filtering theexposed coal ash comprises cyclone separating the expose coal ash. 6.The method of claim 5, wherein cyclone separating removes coal ash thatis smaller than a second predefined size.
 7. The method of claim 6,wherein the substantially fine portion of the coal ash is smaller thanthe second predefined size.
 8. The method of claim 7, wherein thesubstantially fine portion of the coal ash is removed and used in acement substitute market.
 9. The method of claim 1, wherein thesubstantially coarse portion of the coal ash is treated with a mineralacid.
 10. The method of claim 1, wherein the mineral acid is nitricacid.
 11. The method of claim 1, wherein treating further comprises:heating the mineral acid to approximately 90° C.; and exposing thesubstantially coarse portion, the substantially fine portion, or both tothe mineral acid for at least one hour.
 12. The method of claim 11,wherein exposing the coal ash further comprises additional heating of aresulting solution formed when exposing the coal ash to the mineral acidto generate a more concentrated mixture.
 13. The method of claim 1,wherein the extracting the aqueous mineral acid solution furthercomprises: mixing the aqueous mineral acid solution with tributylphosphate and kerosene; and removing the organic solution from theaqueous mineral acid solution such that the rare earth salts aresubstantially removed along with the organic solution.
 14. The method ofclaim 1, wherein extracting the aqueous mineral acid solution furthercomprises performing a dry extraction, a liquid extraction, or anycombination thereof.
 15. The method of claim 14, wherein the dryextraction is a Soxhlet extraction.
 16. The method of claim 15, whereinthe dry extraction comprises performing continuous extraction of rareearth salts with tributyl phosphate.
 17. The method of claim 1, whereinmixing the organic solution comprises performing multiple cycles ofmixing the organic solution with water until a concentration level ofrare earth salts in the aqueous solution is below a predeterminedthreshold.
 18. The method of claim 1, wherein magnetically treatingfurther comprises ion exchange separation.
 19. The method of claim 18,wherein ion exchange separation leads to rare earth element mixturessuitable to be converted to mixtures of rare earth oxides and raremetals for various applications such as catalyst, magnets, and phosphorapplications.